Process for forming a pattern including on a semiconductor device

ABSTRACT

An objective of this invention is to prevent resist poisoning and sensitivity deterioration in a chemically amplified resist. The chemically amplified resist comprises a base resin, a photoacid generator and a salt exhibiting buffer effect in the base resin.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a chemically amplified resist composition, aprocess for manufacturing a semiconductor device and a patterningprocess.

2. Description of the Prior Art

As a device has become more compact and more accelerated, lithographyusing a short-wavelength light source has been employed because ofimproving resolution. In addition, there has been used a chemicallyamplified resist as a resist material.

Furthermore, the needs for size reduction and acceleration in asemiconductor device require using, besides a copper (Cu)interconnection, a so-called low dielectric constant material. A copperinterconnection is generally formed by a damascene process in which atrench for an interconnection is formed on an insulating film betweeninterconnections, the trench is filled with copper and then excessivecopper in an unwanted area outside the interconnection trench is removedby chemical mechanical polishing (CMP).

There will be described formation of a copper interconnection by adamascene process using a chemically amplified resist. FIG. 10 isprocess cross-sections showing the procedure of a dual damascene processwhere a via-hole and an interconnection trench are simultaneouslyfilled. A process where the interconnection and the via are formed by aso-called via-first process.

First, on a lower interconnection layer 108 are sequentially deposited afirst etching stopper film 107, a first interlayer insulating film 106,a second etching stopper film 105, a second interlayer insulating film104 and a third interlayer insulating film 103. Then, using well-knownlithography and etching technique, a via-hole 111 is formed in the thirdinterlayer insulating film 103, the second interlayer insulating film104, the second etching stopper film 105 and the first interlayerinsulating film 106 (FIG. 10( a)).

Then, an anti-reflection film 102 is formed on the third interlayerinsulating film 103 and the first etching stopper film 107, during whichthe via-hole 111 is partly or totally buried with the anti-reflectionfilm 102. This figure shows that the via-hole 111 is partly buried withthe anti-reflection film 102 (FIG. 10( b)).

Next, on the anti-reflection film 102 is applied a chemically amplifiedresist 201 (FIG. 10( c)). Then, in the chemically amplified resist 201is formed an opening pattern 112 for forming an interconnection trenchconnected to the via-hole 111 (FIG. 10( d)).

Subsequently, using the chemically amplified resist 201 as a mask, theanti-reflection film 102 on the third interlayer insulating film 103,and then the third interlayer insulating film 103 and the secondinterlayer insulating film 104 are etched off to form an interconnectiontrench 113 (FIGS. 10 (e) and (f)).

Then, the chemically amplified resist 201 and the anti-reflection film102 are stripped off by O₂ plasma ashing and using an organic stripper.Next, the first etching stopper film 107 at the bottom of the via-hole111 is etched off to provide a structure where the via-hole 111 isconnected to the upper surface of the interconnection (not shown) in thelower interconnection layer 108 (FIG. 10( g)).

Next, a metal film is formed such that it buries the interconnectiontrench 113 and the via-hole 111. The metal film can be formed by firstforming a barrier metal film within the interconnection trench 113 andthe via-hole 111 by sputtering and then burying the interconnectiontrench 113 and the via-hole 111 with an interconnection metal film by,for example, electroplating. Subsequently, unwanted barrier metal andinterconnection metal films outside the interconnection trench 113 areremoved by CMP to form an interconnection 109 (FIG. 10( h)).

In such a via-first process, defective resolution of the resist on thevia-hole 111 tends to occur during forming the opening pattern 112 inthe chemically amplified resist 201. Such a phenomenon that defectiveresolution is induced in a particular area not due to a lower opticalresolution, but due to an external factor inhibiting resolution of achemically amplified resist is called “resist poisoning”. If resistpoisoning occurs, an interlayer insulating film cannot be processed intoa desired shape. Furthermore, when directly forming an interconnection,interconnection-defects such as stress-migration and electro-migrationmay occur, leading to a less reliable semiconductor device.

To solve the problem, it has been proposed that a resist compositioncomprising an organic base is used for preventing resist poisoning of aresist pattern (Tokkai 2000-137328). Tokkai 2000-137328 has describedthat addition of an organic base is effective for preventing dimensionalfluctuation of a resist pattern because diffusion or activity of an acidafter exposure is inhibited. Hereinafter, an organic base used for sucha purpose is referred to as a “quencher”.

However, when adding a quencher to a resist composition, it is effectivefor preventing resist poisoning during resist patterning, but it maylead to deteriorate in resist sensitivity. A resist with excessivelylower sensitivity may reduce a throughput in an exposure process andthus may sometimes lead to significantly deteriorated mass productivity.For example, a three-fold amount of the quencher requires an almostthree-fold exposure time. Thus, when adding a sufficient amount of thequencher to completely prevent poisoning, an exposure time frequentlyexceed a permissible limit. Furthermore, in a lithography process with alower throughput such as EB direct-drawing lithography, it is difficultto increase the amount of the quencher for preventing resist poisoning.Thus, the process cannot be sometimes employed due to resist poisoning.

In view of the situation, an objective of this invention is to provide atechnique for preventing occurrence of poisoning and deterioration insensitivity in a chemically amplified resist.

We have intensely investigated the above problems, conducting extensiveexperiments, and consequently have found the followings.

In a via-first process described above with reference to FIG. 10, it hasbeen found that sensitivity in a chemically amplified resist may belowered because of the mechanism described below. FIG. 11 is a processcross-section showing occurrence of defective formation of a chemicallyamplified resist on a via-hole.

First, by the above steps illustrated in FIGS. 10( a) to 10(c), achemically amplified resist 201 is applied on an anti-reflection film102. Then, an opening pattern 112 for forming an interconnection trenchis transferred to the chemically amplified resist 201. In the process,as shown in FIG. 11( a), a chemically amplified resist 201 cannot beremoved on and around the upper surface of the via-hole and partlyremains (FIG. 11( a)).

Then, the anti-reflection film 102 is removed (FIG. 11( b)), and thenthe third interlayer insulating film 103 and the second interlayerinsulating film 104 are etched off (FIG. 11( c)). In the process, asshown in FIG. 11( a), the chemically amplified resist 201 remains withinthe opening pattern 112, so that an interconnection trench 113 is notformed in conformity to a pattern and a residual fence 114 of the thirdinterlayer insulating film 103 and the second interlayer insulating film104 is formed on and around the upper surface of the via-hole. Theresidual fence 114 is not removed by subsequent O₂ plasma ashing ortreatment with an organic stripper (FIG. 11( d)), and remains in theinterconnection trench 113 (FIG. 11( e)).

We have further analyzed the cause of a defective pattern in the aboveprocess and have obtained a new finding described below. Specifically,it has been found that an amine or its analogue is formed in aninterlayer insulating film formed on a semiconductor substrate and thecompound is subjected to neutralization with an acid catalyst in achemically amplified resist, leading to deteriorated sensitivity of aresist.

A variety of sources may be deduced for such an amine; for example, anitrogen-containing film formed under a resist, NOx in a deposition gasused for, e.g., depositing a silicon oxide film, or an amine present ina stripper used for removing a resist.

SUMMARY OF THE INVENTION

We have also investigated relationship between tendency to poisoning andthe type of an insulating film and have found that poisoning tends tooccur when using a low dielectric-constant film with a specificdielectric constant of 3 or less. Although the reason has not clearlyunderstood, it may be assumed that such a film has a more porousstructure in comparison with, for example, an SiO₂ film formed by plasmaCVD and thus an amine tends to be easily occluded in the film.

Based on the new findings above described, we have concluded that it isessential to reduce influence of an amine compound present in a systemfor minimizing deterioration of resist sensitivity. Further continuinginvestigation in the light of the concept, we have demonstrated that asalt exhibiting buffer effect can be added to a resist composition tominimize influence of an amine compound and thus to form a stable resistpattern capable of stably preventing poisoning from occurring whilemaintain higher sensitivity.

This invention provides a chemically amplified resist compositioncomprising a base resin; a photoacid generator which generates an acidby exposure; and a salt exhibiting buffer effect in the base resin.

The term, “buffer effect” as used herein means an action of inhibitingfluctuation of a proton concentration in a resist, and keeping theproton concentration constant. When being solidified, a resistcomposition comprising such a salt exhibits equivalent bufferingbehavior in the solid as if the composition is in an aqueous liquid, sothat fluctuation of a proton concentration in a resist is insusceptibleto variation of an acid or base concentration.

The resist composition according to this invention comprises a saltexhibiting buffer effect. Thus, an acid generated from a photoacidgenerator can be effectively utilized without excessive consumption tomaintain higher resist sensitivity. Furthermore, it can preventfluctuation of the amount of an acid present in a system due to invasionof, for example, an external amine. That is, fluctuation of sensitivityor resolution in a resist due to external factors can be minimized. Inaddition, the amount of an acid in a system can be kept constant, sothat a resist having a wide exposure margin can be obtained.

A salt exhibiting buffer effect herein is a substance different from aphotoacid generator. A photoacid generator is a substance which can bedecomposed by light irradiation to consequently generate an acid, whilea salt exhibiting buffer effect can generate an acid-base pair in aresist composition without light irradiation, and thus can behave as ifit is a buffer.

This invention also provides a process for manufacturing a semiconductordevice, comprising the steps of forming a film to be etched on asemiconductor substrate; on the film to be etched, forming a firstresist film patterned in a predetermined shape and using the firstresist film as a mask, etching the film to be etched to form a concave;removing the first resist film; on the film to be etched, applying achemically amplified resist composition, which is then dried to form asecond resist film; patterning the second resist film to form an openingsuch that at least part of the region where the concave has been formedis exposed; and etching the film to be etched or a film formed over orbelow the film, using the patterned second resist film as a mask;wherein the chemically amplified resist composition comprises a baseresin; a photoacid generator which generates an acid by exposure; and asalt exhibiting buffer effect in the base resin.

This invention also provides a process for manufacturing a semiconductordevice, comprising the steps of forming a film to be etched on asemiconductor substrate; applying a chemically amplified resistcomposition on the film to be etched and then drying the composition toform a resist film; patterning the resist film; and etching the film tobe etched, using the patterned the resist film as a mask; wherein thechemically amplified resist composition comprises a base resin; aphotoacid generator which generates an acid by exposure; and a saltexhibiting buffer effect in the base resin.

This invention also provides a process for forming a pattern, comprisingthe steps of applying a chemically amplified resist composition on amaterial to be etched and drying the composition to form a resist film;patterning the resist film; and etching and patterning the material tobe etched, using the patterned resist film as a mask; wherein thechemically amplified resist composition comprises a base resin; aphotoacid generator which generates an acid by exposure; and a saltexhibiting buffer effect in the base resin.

In a process according to this invention, a resist film comprising asalt exhibiting buffer effect in a base resin is used. Thus,deterioration in sensitivity during patterning can be minimized and adesired pattern can be reliably formed.

In this invention, a salt exhibiting buffer effect can be prepared byreaction between an acid and a base. Hereinafter, such an acid and abase are referred to as a “salt-forming acid” and a “salt-forming base”,respectively. In this invention, a salt-forming acid may include an acidgenerated from the above photoacid generator by exposure. Thus,buffering action in a resist composition can be ensured to reliablyimprove sensitivity during patterning.

In this invention, the salt may be a sulfonate, which allowsdeterioration in a resist pattern to be further reliably inhibited.

In this invention, the salt may include a basic compound which can beused as a quencher. Herein, a basic compound which can be used as aquencher means a compound which inhibits diffusion of an acid generatedfrom a photoacid generator in a resist film; for example, anitrogen-containing basic compound. Such a basic compound may be used tominimize fluctuation of resolution in patterning and to form reliably adesired pattern. In this invention, the salt may be an amine. Thus,deterioration in sensitivity in a resist can be more reliably prevented.

In this invention, a salt of an alkanolamine with a sulfonic acid can beused as the salt. The sulfonic acid preferably may includebenzenesulfonic acid, alkylsulfonic acid, camphorsulfonic acid and thesesubstituted derivatives. Substituted derivatives include mono andpoly-substituted derivatives, those substituted with an organic groupsuch as alkyl and alkoxy, and those substituted with a halogen such asfluorine, as well as those substituted with a fluoroalkyl. Whenintroducing a substituent such as alkyl and alkoxy, it is preferable toselect the proper carbon number. For example, a substituent with up tothree carbon atoms may give a product having good handling properties.

A salt constituted with the above combination may be used to furtherreliably exert buffering action and thus to further reliably preventsensitivity deterioration in lithography.

In this invention, an alkali solubility of the base resin may be variedby the action of the acid. In a negative resist, a generated acid causesa crosslinking reaction to form a site with a reduced solubility in adeveloper. In a positive resist, a generated acid dissociates aprotective group in a resin to improve solubility. Thus, for example ina chemically amplified resist composition of this invention, the baseresin may have an alkali-soluble group protected with adissolution-inhibiting group and the dissolution-inhibiting group may bedissociated by the action of the acid to give an alkali-soluble resin. Aresist composition according to this invention comprises a saltexhibiting buffer effect, so that when using such a base resin,fluctuation of alkali solubility due to variation in exposure can beprevented.

In a process for manufacturing a semiconductor device of this invention,the step of removing a first resist film may comprise removing a part ofthe first resist film using an amine stripper. In the manufacturingprocess of this invention, a second resist film comprising a saltexhibiting buffer effect is formed. Thus, deterioration in sensitivitycan be reliably prevented when an amine component present in a stripperused for removing the first resist film remains in a film to be etchedand permeates into the second resist film.

In a process for manufacturing a semiconductor device of this invention,the film to be etched may contain nitrogen. In a process for forming apattern of this invention, the material to be etched may containnitrogen. In a manufacturing process of this invention, a resist filmcomprising a salt exhibiting buffer effect is formed. Thus,deterioration in sensitivity can be reliably prevented when anitrogen-containing basic compound derived from a film to be etched oran etching agent permeates into a resist film.

In a process for manufacturing a semiconductor device of this invention,the film to be etched may include a film having a porous structure witha specific dielectric constant of 3 or less. In a process for forming apattern of this invention, the material to be etched may include a filmhaving a porous structure with a specific dielectric constant of 3 orless.

Examples of a “film having a porous structure” include an HSQ film, anMSQ film, an MHSQ film, a ladder-like hydrogenated siloxane film, anSiLK® film, an SiOF film, an SiOC film, an SiON film and abenzocyclobutene film. These films have a relatively bulky substituent,so that they have a free volume larger than a compared with a non-porousfilm represented by an SiO₂ film and may, therefore, have a microporousstructure. In such a film, an amine compound present in a system maytend to be occluded into the film.

Such a film having a porous structure tends to have a lower specificdielectric constant than a non-porous film. Any of the above-describedfilms having a specific dielectric constant of 3 or less may have amicroporous structure.

In this invention, a resist film comprising a salt exhibiting buffereffect is used. Thus, deterioration in sensitivity can be suitablyprevented when an amine compound occluded into a film to be etchedpermeates into a resist film.

In this invention, a film to be etched may be a monolayer ormultilayered film.

Although a configuration of this invention has been described, anyappropriate combination of various components and modification of thisinvention to another category are effective as aspects of thisinvention. For example, a resist film formed by applying and drying theabove chemically amplified resist composition or a wafer on which theresist film is applied may be effective as aspects of this invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view showing a process for manufacturing asemiconductor device according to an embodiment.

FIG. 2 is a cross-sectional view showing a process for manufacturing asemiconductor device according to an embodiment.

FIG. 3 is a cross-sectional view showing a process for manufacturing asemiconductor device according to an embodiment.

FIG. 4 shows a titration curve in an example.

FIG. 5 is a partial enlarged view of FIG. 4.

FIG. 6 shows calculated and experimental values of ΔpH for examples.

FIG. 7 shows a titration curve for an example.

FIG. 8 is a partial enlarged view of FIG. 7.

FIG. 9 shows an SEM photograph for an interconnection trench pattern inan example.

FIG. 10 is a cross-sectional view showing a process for manufacturing asemiconductor device according to the prior art.

FIG. 11 is a cross-sectional view showing a process for manufacturing asemiconductor device according to the prior art.

In these drawings, the symbols have the following meanings; 101:chemically amplified resist, 102: anti-reflection film, 103: thirdinterlayer insulating film, 104: second interlayer insulating film, 105:second etching stopper film, 106: first interlayer insulating film, 107:first etching stopper film, 108: lower interconnection layer, 109:interconnection, 111: via-hole, 112: opening pattern, 113:interconnection trench, 114: residual fence, 115: interlayer insulatingfilm, 116: first resist film, 117: second resist film, 118: third resistfilm, 119: opening pattern, 120: barrier metal film, 121: copper film,122: opening pattern, and 201: chemically amplified resist.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

There will be described components constituting a chemically amplifiedresist according to this invention.

In this invention, a base resin used is a resin whose alkali solubilityvaries by the action of an acid and which is transparent at a wavelengthof a light source used in lithography. A material having a side chainsusceptible to acid hydrolysis is used, to ensure an adequate solubilitydifference in a developing solution before and after exposure.

Specifically, it may be appropriately selected from known materialscommonly used for a chemically amplified resist. For example, a positiveresist composition can comprise a base resin having an acidic functionalgroup protected with a dissolution-inhibiting group which isalkali-insoluble or alkali-poorly-soluble and which becomesalkali-soluble after removing the dissolution-inhibiting group. Anegative resist composition may comprise an alkali-soluble base resinwhich becomes alkali-poorly-soluble by crosslinking by the action of acrosslinking agent. The term, “alkali-insoluble” or“alkali-poorly-soluble” as used herein means that dissolution rate in a2.38 wt % aqueous solution of TMAH (tetramethylammonium hydroxide) isless than 20 Å/sec while “alkali-soluble” means that it is from 20 to300 Å/sec.

Examples of a base resin for a KrF excimer laser resist at a wavelengthof 248 nm, an EUV resist at a wavelength of 3 to 20 nm, an EB resist ora X-ray resist include polyhydroxystyrene (PHS), and a copolymer ofhydroxystrene with one or more monomers such as styrene, (meth)acrylatesand the like. Examples of a base resin for an ArF excimer laser resistat a wavelength of 193 nm include poly(meth)acrylates, alternatingcopolymers of norbornene and maleic anhydride, polynorbornenes andmetathesis ring-opened polymers. Examples of a base resin for an F₂excimer laser at a wavelength of 157 nm include the above-mentionedpolymers which are fluorinated. However, the base resin is not limitedto these polymers.

The term, “(meth)acrylic acid” and (meth)acrylate” as used herein refersto methacrylic acid or acrylic acid, and methacrylate or acrylate,respectively. A base resin used in a positive resist composition is abase resin in which the hydrogen in a phenolic or carboxylic hydroxygroup is replaced with a dissolution-inhibiting group. Generally, suchreplacement reduces a dissolution rate in an unexposed area.

A dissolution-inhibiting group in a base resin may be selected from agroup of, for example, a tertiary alkyl group having 4 to 40 carbonatoms, a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkylgroup having 4 to 20 carbon atoms and so on.

Specifically, examples of a dissolution-inhibiting group include, forexample, tert-butoxycarbonyl, tert-butoxycarbonylmethyl,tert-amyloxycarbonyl, tert-amyloxycarbonylmethyl,1-ethoxyethoxycarbonylmethyl, 2-tetrahydropyranyloxycarbonylmethyl and2-tetrahydrofuranyloxycarbonylmethyl; straight or branched acetals suchas 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-isopropoxyethyl,1-n-butoxyethyl, 1-isobutoxyethyl, 1-sec-butoxyethyl,1-tert-butoxyethyl, 1-tert-amyloxyethyl, 1-cyclohexyloxyethyl,1-methoxypropyl, 1-ethoxypropyl, 1-methoxy-1-methylethyl and1-ethoxy-1-methylethyl; and cyclic acetals such as tetrahydrofuranyl andtetrahydropyranyl, preferably 1-ethoxyethyl, 1-n-butoxyethyl and1-ethoxypropyl.

Alternatively, 0.1% or more of hydrogen atoms in hydroxy groups in abase resin may be inter-molecularly or intra-molecularly crosslinked viaa crosslinking group.

A weight-average molecular weight of a base resin is preferably about5×10³ to 1×10⁵. A molecular weight of less than 5×10³ may lead toinsufficient coatability or resolution, while a molecular weight of morethan 1×10⁵ may lead to deteriorated resolution.

In this invention, a photoacid generator used may be a compound whichgenerates an acid by irradiation of a high energy beam. Depending on thetype of a light source, it may be appropriately selected from knownmaterials. For example, for a KrF resist, it may be selected from asulfonium salt, an iodonium salt, a sulfonyldiazomethanes and anN-sulfonyloxyimide type acid generator, which may be used alone or incombination of two or more.

A sulfonium salt is a salt of a sulfonium cation with a sulfonate.Examples of a sulfonium cation include triphenylsulfonium,(4-tert-butoxyphenyl)diphenylsulfonium,bis(4-tert-butoxyphenyl)phenylsulfonium,tris(4-tert-butoxyphenyl)sulfonium,(3-tert-butoxyphenyl)diphenylsulfonium,bis(3-tert-butoxyphenyl)phenylsulfonium,tris(3-tert-butoxyphenyl)sulfonium,(3,4-di-tert-butoxyphenyl)diphenylsulfonium,bis(3,4-di-tert-butoxyphenyl)phenylsulfonium,tris(3,4-di-tert-butoxyphenyl)sulfonium,diphenyl(4-thiophenoxyphenyl)sulfonium,(4-tert-butoxycarbonylmethyloxyphenyl)diphenylsulfonium,tris(4-tert-butoxycarbonylmethyloxyphenyl)sulfonium,(4-tert-butoxyphenyl)bis(4-dimethylaminophenyl)sulfonium,tris(4-dimethylaminophenyl)sulfonium, 2-naphthyldiphenylsulfonium,dimethyl(2-naphthyl)sulfonium, 4-hydroxyphenyldimethylsulfonium,4-methoxyphenyldimethylsulfonium, trimethylsulfonium,2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium andtribenzylsulfonium cations.

Examples of a sulfonate include trifluoromethanesulfonate,nonafluorobutanesulfonate, heptadecafluorooctanesulfonate,2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate,4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate,toluenesulfonate, benzenesulfonate,4-(4-toluenesulfonyloxy)benzenesulfonate, naphthalenesulfonate,camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate,butanesulfonate and methanesulfonate. A sulfonium salt as a combinationof these may be used.

An iodonium salt is a salt of iodonium cation with a sulfonate. Examplesof an iodonium cation include aryliodonium cations such asdiphenyliodonium, bis(4-tert-butylphenyl)iodonium,4-tert-butoxyphenylphenyliodonium and 4-methoxyphenylphenyliodonium.

Examples of a sulfonate include trifluoromethanesulfonate,nonafluorobutanesulfonate, heptadecafluorooctanesulfonate,2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate,4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate,toluenesulfonate, benzenesulfonate,4-(4-toluenesulfonyloxy)benzenesulfonate, naphthalenesulfonate,camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate,butanesulfonate and methanesulfonate. An iodonium salt as a combinationof these may be used.

Examples of a sulfonyldiazomethane include bissulfonyldiazomethanes suchas bis(ethylsulfonyl)diazomethane,bis(1-methylpropylsulfonyl)diazomethane,bis(2-methylpropylsulfonyl)diazomethane,bis(,1-dimethylethylsulfonyl)diazomethane,bis(cyclohexylsulfonyl)diazomethane,bis(perfluoroisopropylsulfonyl)diazomethane,bis(phenylsulfonyl)diazomethane,bis(4-methylphenylsulfonyl)diazomethane,bis(2,4-dimethylphenylsulfonyl)diazomethane, andbis(2-naphthylsulfonyl)diazomethane, sulfonylcarbonyldiazomethanes suchas 4-methylphenylsulfonylbenzoyldiazomethane,tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane,2-naphthylsulfonylbenzoyidiazomethane,4-methylphenylsulfonyl-2-naphthoyidiazomethane,methylsulfonylbenzoyidiazomethane, and,tert-butoxycarbonyl-4-methylphenylsulfonyldiazomethane, and so on.

Examples of an N-sulfonyloxyimide type photoacid generator include acombination of a moiety of an imide such as succinimide,naphthalenedicarboxylic imide, phathalimide, cyclohexyldicarboxylicimide, 5-norbornene-2,3-dicarboxylic imide,7-oxabicyclo[2.2.1]-5-heptene-2,3-dicarboxylic imide with a sulfonatesuch as trifluoromethanesulfonate, nonafluorobutanesulfonate,heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate,pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate,4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate,naphthalenesulfonate, camphorsulfonate, octanesulfonate,dodecylbenzenesulfonate, butanesulfonate and methanesulfonate.

Examples of a benzoinsulfonate type photoacid generator include benzointosylate, benzoin mesylate and benzoin butanesulfonate.

Examples of a pyrogallol trisulfonate type photoacid generator includepyrogallol, phloroglucinol, catechol, resorcinol and hydroquinonederivatives, all of whose hydroxyl groups are replaced with anappropriate sulfonate such as trifluoromethanesulfonate,nonafluorobutanesulfonate, heptadecafluorooctanesulfonate,2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate,4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate,toluenesulfonate, benzenesulfonate, naphthalenesulfonate,camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate,butanesulfonate and methanesulfonate.

Examples of a nitrobenzylsulfonate type photoacid generator include2,4-dinitrobenzylsulfonate, 2-nitrobenzylsulfonate and2,6-dinitrobenzylsulfonate. Examples of a sulfonate includetrifluoromethanesulfonate, nonafluorobutanesulfonate,heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate,pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate,4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate,naphthalenesulfonate, camphorsulfonate, octanesulfonate,dodecylbenzenesulfonate, butanesulfonate and methanesulfonate.Alternatively, a compound whose nitro group substituted to the benzylmoiety is replaced with a trifluoromethyl group may be used as same as anitro benzylsulfonate type photoacid generator.

Examples of a sulfone type photoacid generator includebis(phenylsulfonyl)methane, bis(4-methylphenylsulfonyl)methane,bis(2-naphthylsulfonyl)methane, 2,2-bis(phenylsulfonyl)propane,2,2-bis(4-methylphenylsulfonyl)propane,2,2-bis(2-naphthylsulfonyl)propane,2-methyl-2-(p-toluenesulfonyl)propiophenone,2-(cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane,2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one and so on.

Examples of a glyoxime derivative type photoacid generator includeO,O′-bis(p-toluenesulfonyl)-α-dimethylglyoxime,O,O′-bis(p-toluenesulfonyl)-α-diphenylglyoxime,O,O′-bis(p-toluenesulfonyl)-α-dicyclohexylglyoxime,O,O′-bis(p-toluenesulfonyl)-2,3-pentanedioneglyoxime,O,O′-bis(p-toluenesulfonyl)-2-methyl-3,4-pentanedioneglyoxime,O,O′-bis(n-butanesulfonyl)-α-dimethylglyoxime,O,O′-bis(n-butanesulfonyl)-α-diphenylglyoxime,O,O′-bis(n-butanesulfonyl)-α-dicyclohexylglyoxime,O,O′-bis(n-butanesulfonyl)-2,3-pentanedioneglyoxime,O,O′-bis(n-butanesulfonyl)-2-methyl-3,4-pentanedioneglyoxime,O,O′-bis(methanesulfonyl)-α-dimethylglyoxime,O,O′-bis(trifluoromethanesulfonyl)-α-dimethylglyoxime,O,O′-bis(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime,O,O′-bis(tert-butanesulfonyl)-α-dimethylglyoxime,O,O′-bis(perfluorooctanesulfonyl)-α-dimethylglyoxime,O,O′-bis(cyclohexylsulfonyl)-α-dimethylglyoxime,O,O′-bis(benzenesulfonyl)-α-dimethylglyoxime,O,O′-bis(p-fluorobenzenesulfonyl)-α-dimethylglyoxime,O,O′-bis(p-tert-butyl benzenesulfonyl)-α-dimethylglyoxime,O,O′-bis(xylenesulfonyl)-α-dimethylglyoxime andO,O′-bis(camphorsulfonyl)-α-dimethylglyoxime.

Among others, a preferable photoacid generator is a sulfonium salt, abissulfonyldiazomethane and an N-sulfonyloxyimide type photoacidgenerator.

Photoacid generators may be used alone or in combination of two or more.

A content of an acid generator is preferably 0.2 to 50 wt parts,particularly 0.5 to 40 wt parts to 100 wt parts of the total base resin.If it is less than 0.2 wt parts, an inadequate amount of an acid may begenerated during exposure, leading to deteriorated sensitivity orresolution. If it is more than 50 wt parts, a transparency of a resistmay be too low to provide adequate resolution.

A resist composition of this invention may contain a quencher, withwhich poisoning in a resist can be suitably prevented. A suitablequencher is a compound which reduces a diffusion rate of an acidgenerated from a photoacid generator in a resist film. Such a materialcan be added to reduce a diffusion rate of an acid in a resist film,resulting in improved resolution; to minimize fluctuation of sensitivityafter exposure; and to minimize substrate- or environment-dependency toimprove exposure margin or pattern profile.

A quencher is suitably a basic compound including ammonia; primary,secondary and tertiary aliphatic amines; mixed amines; aromatic amines;heterocyclic amines; nitrogen-containing compounds having carboxyl;nitrogen-containing compounds having sulfonyl; nitrogen-containingcompounds having hydroxy; nitrogen-containing compounds havinghydroxyphenyl; alcoholic nitrogen-containing compounds; amidederivatives; and imide derivatives.

Examples of a primary aliphatic amine include methylamine, ethylamine,n-propylamine, isopropylamine, n-butylamine, isobutylamine,sec-butylamine, tert-butylamine, pentylamine, tert-amylamine,cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine,nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine,ethylenediamine and tetraethylenepentamine. Examples of a secondaryaliphatic amine include dimethylamine, diethylamine, di-n-propylamine,diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine,dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine,diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine,dicetylamine, N,N′-dimethylmethylenediamine,N,N′-dimethylethylenediamine and N,N″″-dimethyltetraethylenepentamine.Examples of a tertiary aliphatic amine include trimethylamine,triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine,triisobutylamine, tri-sec-butylamine, tripentylamine,tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine,trioctylamine, trinonylamine, tridecylamine, tridodecylamine,tricetylamine, N,N,N′,N′-tetramethylmethylenediamine,N,N,N′,N′-tetramethylethylenediamine andN,N,N″″,N″″-tetramethyltetraethylenepentamine.

Examples of a mixed amine include dimethylethylamine,methylethylpropylamine, benzylamine, phenetylamine andbenzyldimethylamine. Examples of an aromatic or heterocyclic amineinclude anilines such as aniline, N-methylaniline, N-ethylaniline,N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline,4-methylaniline, ethylaniline, propylaniline, trimethylaniline,2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline,2,6-dinitroaniline, 3,5-dinitroaniline and N,N-dimethyltoluidine;diphenyl(p-tolyl)amine; methyldiphenylamine; triphenylamine;phenylenediamine; naphthylamine; diaminonaphthalene; pyrroles such aspyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole,2,5-dimethylpyrrole and N-methylpyrrole; oxazoles such as oxazole andisoxazole; thiazoles such as thiazole and isothiazole; imidazoles suchas imidazole, 4-methylimidazole and 4-methyl-2-phenylimidazole;pyrazoles; furazans; pyrrolines such as pyrroline and2-methyl-1-pyrroline; pyrrolidines such as pyrrolidine,N-methylpyrrolidine, pyrrolidinone and N-methylpyrrolidone;imidazolines; imidazolidines; pyridines such as pyridine,methylpyridine, ethylpyridine, propylpyridine, butylpyridine,4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine,triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine,4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine,butoxypyridine, dimethoxypyridine, 4-pyrrolidinopyridine,2-(1-ethylpropyl)pyridine, aminopyridine and dimethylaminopyridine;pyridazines; pyrimidines; pyrazines; pyrazolines; pyrazolidines;piperidines; piperazines; morpholines; indoles; isoindoles;1H-indazoles; indolines; quinolines such as quinoline and3-quinolinecarbonitrile; isoquinolines; cinnolines; quinazolines;quinoxalines; phthalazines; purines; pteridines; carbazoles;phenanthridines; acridines; phenazine; 1,10-phenanthrolines; adenines;adenosines; guanines; guanosines; uracils; uridines, and so on.

Examples of a nitrogen-containing compound having a carboxyl groupinclude aminobenzoic acids; indole carboxylic acids; amino acidderivatives such as nicotinic acid, alanine, arginine, aspartic acid,glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine,methionine, phenylalanine, threonine, lysine,3-aminopyrazine-2-carboxylic acid and methoxyalanine, and so on.

Examples of a nitrogen-containing compound having a sulfonyl groupinclude 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, and soon.

Examples of a nitrogen-containing compound having a hydroxy group, anitrogen-containing compound having a hydroxyphenyl group or analcoholic nitrogen-containing compound include 2-hydroxypyridine,aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate,monoethanolamine, diethanolamine, triethanolamine,N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine,2,2′-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol,4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine,2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine,1-[2-(2-hydroxyethoxy)ethyl]piperazine, piperidineethanol,1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidinone,3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol,8-hydroxyyulolidine, 3-quinuclidinol, 3-tropanol,1-methyl-2-pyrrolidineethanol, 1-aziridineethanol,N-(2-hydroxyethyl)phthalimide, N-(2-hydroxyethyl)isonicotinamide and soon.

Examples of an amide include formamide, N-methylformamide,N,N-dimethylformamide, acetamide, N-methylacetamide,N,N-dimethylacetamide, propionamide, benzamide and so on.

Examples of an imide include phthalimide, succinimide, maleimide and soon.

Other examples which can be used as a quencher includetris(2-methoxymethoxyethyl)amine, tris[2-(2-methoxyethoxy)ethyl]amine,tris[2-(2-methoxyethoxymethoxy)ethyl]amine,tris[2-(1-methoxyethoxy)ethyl]amine, tris[2-(1-ethoxyethoxy)ethyl]amine,tris[2-(1-ethoxypropoxy)ethyl]amine,tris{2-[2-(2-hydroxyethoxy)ethoxy]ethyl}amine,4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane,4,7,13,18-tetraoxa-1,10-diazabicyclo[8.5.5]eicosane,1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane,1-aza-12-crown-4,1-aza-15-crown-5,1-aza-18-crown-6,tris(2-formyloxyethyl)amine, tris(2-acetoxyethyl)amine,tris(2-propionyloxyethyl)amine, tris(2-butyryloxyethyl)amine,tris(2-isobutyryloxyethyl)amine, tris(2-valeryloxyethyl)amine,tris(2-pivaloyloxyethyl)amine,N,N-bis(2-acetoxyethyl)-2-(acetoxyacetoxy)ethylamine,tris(2-methoxycarbonyloxyethyl)amine,tris(2-tert-butoxycarbonyloxyethyl)amine,tris[2-(2-oxopropoxy)ethyl]amine,tris[2-(methoxycarbonylmethyl)oxyethyl]amine,tris[2-(tert-butoxycarbonylmethyloxy)ethyl]amine,tris[2-(cyclohexyloxycarbonylmethyloxy)ethyl]amine,tris(2-methoxycarbonylethyl)amine, tris(2-ethoxycarbonylethyl)amine,N,N-bis(2-hydroxyethyl)-2-(methoxycarbonyl)ethylamine,N,N-bis(2-acetoxyethyl)-2-(methoxycarbonyl)ethylamine,N,N-bis(2-hydroxyethyl)-2-(ethoxycarbonyl)ethylamine,N,N-bis(2-acetoxyethyl)-2-(ethoxycarbonyl)ethylamine,N,N-bis(2-hydroxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine,N,N-bis(2-acetoxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine,N,N-bis(2-hydroxyethyl)-2-(2-hydroxyethoxycarbonyl)ethylamine,N,N-bis(2-acetoxyethyl)-2-(2-acetoxyethoxycarbonyl)ethylamine,N,N-bis(2-hydroxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]ethylamine,N,N-bis(2-acetoxyethyl)₂-[(methoxycarbonyl)methoxycarbonyl]ethylamine,N,N-bis(2-hydroxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine,N,N-bis(2-acetoxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine,N,N-bis(2-hydroxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)ethylamine,N,N-bis(2-acetoxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)ethylamine,N,N-bis(2-hydroxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine,N,N-bis(2-acetoxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine,N,N-bis(2-hydroxyethyl)-2-(4-hydroxybutoxycarbonyl)ethylamine,N,N-bis(2-formyloxyethyl)-2-(4-formyloxybutoxycarbonyl)ethylamine,N,N-bis(2-formyloxyethyl)-2-(2-formyloxyethoxycarbonyl)ethylamine,N,N-bis(2-methoxyethyl)-2-(methoxycarbonyl)ethylamine,N-(2-hydroxyethyl)bis[2-(methoxycarbonyl)ethyl]amine,N-(2-acetoxyethyl)bis[2-(methoxycarbonyl)ethyl]amine,N-(2-hydroxyethyl)bis[2-(ethoxycarbonyl)ethyl]amine,N-(2-acetoxyethyl)bis[2-(ethoxycarbonyl)ethyl]amine,N-(3-hydroxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine,N-(3-acetoxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine,N-(2-methoxyethyl)bis[2-(methoxycarbonyl)ethyl]amine,N-butylbis[2-(methoxycarbonyl)ethyl]amine,N-butylbis[2-(2-methoxyethoxycarbonyl)ethyl]amine,N-methylbis(2-acetoxyethyl)amine, N-ethylbis(2-acetoxyethyl)amine,N-methylbis(2-pivaloyloxyethyl)amine,N-ethylbis[2-(methoxycarbonyloxy)ethyl]amine,N-ethylbis[2-(tert-butoxycarbonyloxy)ethyl]amine,tris(methoxycarbonylmethyl)amine, tris(ethoxycarbonylmethyl)amine,N-butylbis(methoxycarbonylmethyl)amine,N-hexylbis(methoxycarbonylmethyl)amine, β-(diethylamino)-δ-valerolactoneand so on.

Quenchers may be used alone or in combination of two or more.

Their content is suitably 0 to 2 wt parts, particularly 0.01 to 1 wtpart to 100 wt parts of the solid in a resist material. If it is morethan 2 wt parts, sensitivity may be excessively lowered.

In this invention, a salt exhibiting buffer effect may be preferably acompound which can prevent fluctuation of a proton concentration in aresist to keep the concentration constant as if equilibrium isestablished in the resist. Particularly preferably, a resist compositioncomprises an anion of an acid generated from a photoacid generator orits substituted derivative, to effectively prevent fluctuation of aproton concentration in the resist. Thus, for example, fluctuation of aproton concentration can be prevented when an organic base such as anamine permeates into a resist composition.

An acid in a photoacid generator may be an acid having a less volatileanion or an anion which is not extremely diffusible. Examples of asuitable anion herein include benzenesulfonate anion, toluenesulfonateanion, xylenesulfonate anion, 4-chlorobenzenesulfonate anion,4-(4-toluenesulfonyloxy)benzenesulfonate anion,pentafluorobenzenesulfonate anion, tert-butanesulfonate anion,2,2,2-trifluoroethanesulfonate anion, nonafluorobutanesulfonate anion,heptadecafluorooctanesulfonate anion and camphorsulfonate anion. It maybe preferably selected from, for example, the acids represented bygeneral formulas (A) to (E).

A salt exhibiting buffer effect may comprise any of the bases or theirsubstituted derivatives which can be used as a quencher, to reliablyimprove resolution of a resist pattern. Such a base may be, for example,suitably an amine.

Examples of a base which can be used as a quencher include amines suchas 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanolhydrate, monoethanolamine, diethanolamine, triethanolamine,N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine,2,2′-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol,4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine,2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine,1-[2-(2-hydroxyethoxy)ethyl]piperazine, piperidineethanol,1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidinone,3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol,8-hydroxyyulolidine, 3-quinuclidinol, 3-tropanol,1-methyl-2-pyrrolidineethanol, 1-aziridineethanol,tris(2-methoxymethoxyethyl)amine, tris(2-(2-methoxyethoxy)ethyl)amine,tris(2-(2-methoxyethoxymethoxy)ethyl)amine,tris(2-(1-methoxyethoxy)ethyl)amine, tris(2-(1-ethoxyethoxy)ethyl)amine,tris(2-(1-ethoxypropoxy)ethyl)amine,tris[2-(2-(2-hydroxyethoxy)ethoxy)ethyl]amine,tris(2-formyloxyethyl)amine, tris(2-acetoxyethylamine,tris(2-propionyloxyethyl)amine, tris(2-butyryloxyethyl)amine,tris(2-isobutyryloxyethyl)amine, tris(2-valeryloxyethyl)amine,tris(2-pivaloyloxyethyl)amine,N,N-bis(2-acetoxyethyl)-2-(acetoxyacetoxy)ethylamine,tris(2-methoxycarbonyloxyethyl)amine,tris(2-tert-butoxycarbonyloxyethyl)amine,tris[2-(2-oxopropoxy)ethyl]amine,tris[2-(methoxycarbonylmethyl)oxyethyl]amine,tris[2-(tert-butoxycarbonylmethyloxy)ethyl]amine,tris[2-(cyclohexyloxycarbonylmethyloxy)ethyl]amine,tris(2-methoxycarbonylethyl)amine, tris(2-ethoxycarbonylethyl)amine,N,N-bis(2-hydroxyethyl)-2-(methoxycarbonyl)ethylamine,N,N-bis(2-acetoxyethyl)-2-(methoxycarbonyl)ethylamine,N,N-bis(2-hydroxyethyl)-2-(ethoxycarbonyl)ethylamine,N,N-bis(2-acetoxyethyl)-2-(ethoxycarbonyl)ethyl amine,N,N-bis(2-hydroxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine,N,N-bis(2-acetoxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine,N,N-bis(2-hydroxyethyl)-2-(2-hydroxyethoxycarbonyl)ethylamine,N,N-bis(2-acetoxyethyl)-2-(2-acetoxyethoxycarbonyl)ethylamine,N,N-bis(2-hydroxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]ethylamine,N,N-bis(2-acetoxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]ethylamine,N,N-bis(2-hydroxyethyl)2-(2-oxopropoxycarbonyl)ethylamine,N,N-bis(2-acetoxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine,N,N-bis(2-hydroxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)ethylamine,N,N-bis(2-acetoxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)ethylamine,N,N-bis(2-hydroxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine,N,N-bis(2-acetoxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine,N,N-bis(2-hydroxyethyl)-2-(4-hydroxybutoxycarbonyl)ethylamine,N,N-bis(2-formyloxyethyl)-2-(4-formyloxybutoxycarbonyl)ethylamine,N,N-bis(2-formyloxyethyl)-2-(2-formyloxyethoxycarbonyl)ethylamine,N,N-bis(2-methoxyethyl)-2-(methoxycarbonyl)ethylamine,N-(2-hydroxyethyl)bis[2-(methoxycarbonyl)ethyl]amine,N-(2-acetoxyethyl)bis[2-(methoxycarbonyl)ethyl]amine,N-(2-hydroxyethyl)bis[2-(ethoxycarbonyl)ethyl]amine,N-(2-acetoxyethyl)bis[2-(ethoxycarbonyl)ethyl]amine,N-(3-hydroxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine,N-(3-acetoxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine,N-(2-methoxyethyl)bis[2-(methoxycarbonyl)ethyl]amine,N-butylbis[2-(methoxycarbonyl)ethyl]amine,N-butylbis[2-(2-methoxyethoxycarbonyl)ethyl]amine,N-methylbis(2-acetoxyethyl)amine, N-ethylbis(2-acetoxyethyl)amine,N-methylbis(2-pivaloyloxyethyl)amine,N-ethylbis[2-(methoxycarbonyloxy)ethyl]amine,N-ethylbis[2-(tert-butoxycarbonyloxy)ethyl]amine,tris(methoxycarbonylmethyl)amine, tris(ethoxycarbonylmethyl)amine,N-butylbis(methoxycarbonylmethyl)amine,N-hexylbis(methoxycarbonylmethyl)amine andβ-(diethylamino)-δ-valerolactone.

A preferable salt exhibiting buffer effect is a salt of sulfonic acidwith alkanolamine or alkoxyalkylamine. Specific compounds may be thoserepresented by formulas (F) to (H), which can be used to reliablyimprove sensitivity during forming a resist pattern.

t-BuSO₃HN(C₂H₄CH)₃  (F)

C₄F₉SO₃HN(CH₂CCH₃)₃  (G)

An acid constituting a salt exhibiting buffer effect is preferably asubstance whose pKa (25° C.) is from 3 to 12 in acetonitrile. Such asubstance can be added to a resist composition to achieve adequatebuffer effect for reliable resist performance.

A content of a salt exhibiting buffer effect in a resist composition isnot particularly limited as long as it is adequate to exert buffereffect, and for example, is not less than 0.001 wt parts, preferably notless than 0.01 wt parts to 100 wt parts of a solid in the resistcomposition. Thus, buffer effect can be ensured in the resistcomposition. The salt exhibiting buffer effect may be contained at up to30 wt parts, preferably up to 10 wt parts to 100 wt parts of a solid inthe resist composition. Thus, a desirable resist shape can be reliablyformed.

When adding a salt exhibiting buffer effect to a resist composition, itmay be added after being formed as a salt, or may be added as a mixedsolution prepared by mixing an acid and a base in an organic solvent.

A resist composition of this invention may contain an organic solvent,which may be capable of dissolving a photoacid generator and a baseresin. Examples of such an organic solvent include, but not limited to,ketones such as cyclohexanone and methyl-n-amylketone; alcohols such as3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol and1-ethoxy-2-propanol; ethers such as propyleneglycolmonomethyl ether,ethyleneglycolmonomethyl ether, propyleneglycolmonoethyl ether,ethyleneglycolmonoethyl ether, propyleneglycoldimethyl ether anddiethyleneglycoldimethyl ether; and esters such aspropyleneglycolmonomethyl ether acetate, propyleneglycolmonoethyl etheracetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate,tert-butyl propionate and propyleneglycol-mono-tert-butyl ether acetate,which can be used alone or in combination of two or more. Among these,organic solvents preferably used in this invention arediethyleneglycoldimethyl ether, 1-ethoxy-2-propanol and ethyl lactatewhich exhibit the highest ability of dissolving an acid generator in aresist composition, and propyleneglycolmonomethyl ether acetate which isa safe solvent, as well as mixtures thereof.

When a resist composition of this invention is a negative type, it maycomprise a crosslinking agent, which may be a compound having two ormore intramolecular hydroxymethyl, alkoxymethyl, epoxy or vinyl ethergroups.

Suitable examples may include substituted glycolurils, ureas andhexa(methoxymethyl)melamine. Specific examples includeN,N,N′,N′-tetramethoxymethylurea, hexamethylmelamine;tetrahydroxymethylglycoluril; tetraalkoxymethyl-substituted glycolurilssuch as tetramethoxymethylglycoluril; and condensation products of aphenol compound (e.g., bis(hydroxymethylphenol)s and bisphenol-A) withepichlorohydrin. Particularly suitable crosslinking agents include1,3,4,6-tetrahydroxymethylglycoluril,1,3,4,6-tetraalkoxymethylglycolurils such as1,3,4,6-tetramethoxymethylglycoluril, 2,6-dihydroxymethyl-p-cresol,2,6-dihydroxymethylphenol, 2,2′,6,6′-tetrahydroxymethylbisphenol-A,1,4-bis[2-(2-hydroxypropyl)phenyl]benzene,N,N,N′,N′-tetramethoxymethylurea and hexamethoxymethylmelamine.

A crosslinking agent may preferably initiate crosslinking by an acid.Its content may be appropriately determined, and is generally 1 to 25 wtparts, preferably 5 to 20 wt parts to 100 parts of the total solid in aresist composition. They may be used alone or in combination of two ormore.

When a resist composition of this invention is a positive type, it maycomprise a dissolution inhibitor. A dissolution inhibitor may be acompound having a molecular weight of up to 3×10³ whose solubility in analkali developing solution varies by the action of an acid;particularly, a phenol or carboxylic acid derivative having a lowermolecular weight of up to 2.5×10³, whose functional groups are partly orentirely substituted with an acid-labile substituent.

Examples of a phenol or carboxylic acid derivative having a molecularweight of up to 2.5×10³ includes bisphenol-A, bisphenol-F, bisphenol-S,4,4-bis(4-hydroxyphenyl)valeric acid, tris(4-hydroxyphenyl)methane,1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,2-tris(4-hydroxyphenyl)ethane,phenolphthalein and thymolphthalein. An acid-labile substituent may beselected from dissolution-inhibiting groups for a base resin.

Examples of a suitable dissolution inhibitor includebis[4-(2-tetrahydropyranyloxy)phenyl]methane,bis[4-(2-tetrahydrofuranyloxy)phenyl]methane,bis[4-tert-butoxyphenyl]methane,bis(4-tert-butoxycarbonyloxyphenyl)methane,bis(4-tert-butoxycarbonylmethyloxyphenyl)methane,bis[4-(1-ethoxyethoxy)phenyl]methane,bis[4-(1-ethoxypropyloxy)phenyl]methane,2,2-bis[4-(2-tetrahydropyranyloxy)phenyl]propane,2,2-bis[4-(2-tetrahydrofuranyloxy)phenyl]propane,2,2-bis(4-tert-butoxyphenyl)propane,2,2-bis(4-tert-butoxycarbonyloxyphenyl)propane,2,2-bis(4-tert-butoxycarbonylmethyloxyphenyl)propane,2,2-bis[4-(1-ethoxyethoxy)phenyl]propane,2,2-bis[4-(1-ethoxypropyloxy)phenyl]propane, tert-butyl4,4-bis[4-(2-tetrahydropyranyloxy)phenyl]valerate, tert-butyl4,4-bis[4-(2-tetrahydrofuranyloxy)phenyl]valerate, tert-butyl4,4-bis(4-tert-butoxyphenyl)valerate, tert-butyl4,4-bis(4-tert-butoxycarbonyloxyphenyl)valerate, tert-butyl4,4-bis(4-tert-butoxycarbonylmethyloxyphenyl)valerate, tert-butyl4,4-bis[4-(1-ethoxyethoxy)phenyl]valerate, tert-butyl4,4-bis[4-(1-ethoxypropyloxy)phenyl]valerate,tris[4-(2-tetrahydropyranyloxy)phenyl]methane,tris[4-(2-tetrahydrofuranyloxy)phenyl]methane,tris(4-tert-butoxyphenyl)methane,tris(4-tert-butoxycarbonyloxyphenyl)methane,tris(4-tert-butoxycarbonyloxymethylphenyl)methane,tris[4-(1-ethoxyethoxy)phenyl]methane,tris[4-(1-ethoxypropyloxy)phenyl]methane,1,1,2-tris[4-(2-tetrahydropyranyloxy)phenyl]ethane,1,1,2-tris[4-(2-tetrahydrofuranyloxy)phenyl]ethane,1,1,2-tris(4-tert-butoxyphenyl)ethane,1,1,2-tris(4-tert-butoxycarbonyloxyphenyl)ethane,1,1,2-tris(4-tert-butoxycarbonylmethyloxyphenyl)ethane,1,1,2-tris[4-(1-ethoxyethoxy)phenyl]ethane and1,1,2-tris[4-(1-ethoxypropyloxy)phenyl]ethane.

A content of a dissolution inhibitor in a resist composition used for achemically amplified resist is preferably up to 20 wt parts, morepreferably up to 15 wt parts to 100 wt parts of a solid in the resistmaterial. If it is more than 20 wt parts, increased monomer componentsmay cause deterioration in heat resistance of the resist material.

There will be described a semiconductor process using a resistcomposition according to this invention with reference to the drawings.In the following embodiments, the resist compositions described aboveare used.

Embodiment 1

This embodiment illustrates a dual damascene process employing avia-first method, using a chemically amplified resist composition. FIG.1 is cross-sectional views showing a manufacturing process for asemiconductor device according to this embodiment.

First, on a lower interconnection layer 108 are sequentially deposited afirst etching stopper film 107, a first interlayer insulating film 106,a second etching stopper film 105, a second interlayer insulating film104 and a third interlayer insulating film 103. Then, using well-knownlithography and etching technique, a via-hole 111 is formed in the thirdinterlayer insulating film 103, the second interlayer insulating film104, the second etching stopper film 105 and the first interlayerinsulating film 106 (FIG. 1( a)).

Then, an anti-reflection film 102 is formed on the third interlayerinsulating film 103 and the first etching stopper film 107, during whichthe via-hole 111 is partly or totally buried with the anti-reflectionfilm 102. This figure shows that the via-hole 111 is partly buried withthe anti-reflection film 102 (FIG. 1( b)).

Next, on the anti-reflection film 102 is applied a chemically amplifiedresist 101 (FIG. 1( c)). Then, in the chemically amplified resist 101 isformed an opening pattern 112 for forming an interconnection trenchconnected to the via-hole 111 (FIG. 1( d)). Herein, the resistcomposition described above is used for forming the chemically amplifiedresist 101. Such a resist composition can be used as a chemicallyamplified resist 101 to provide a resist pattern exhibiting improvedsensitivity and resolution when forming an opening pattern 112.

Subsequently, using the chemically amplified resist 101 as a mask, theanti-reflection film 102 on the third interlayer insulating film 103,and then the third interlayer insulating film 103 and the secondinterlayer insulating film 104 are etched off to form an interconnectiontrench 113 (FIGS. 1( e) and (f)).

Then, the chemically amplified resist 101 and the anti-reflection film102 are stripped off by O₂ plasma ashing and using an amine stripper.Next, the first etching stopper film 107 at the bottom of the via-hole111 is etched off to provide a structure where the via-hole 111 isconnected to the upper surface of the interconnection metal (not shown)in the lower interconnection layer 108 (FIG. 1( g)).

Next, a metal film is formed so that it buries the interconnectiontrench 113 and the via-hole 111. The metal film can be formed by firstforming a barrier metal film within the interconnection trench 113 andthe via-hole 111 by sputtering and then burying the interconnectiontrench 113 and the via-hole 111 with an interconnection metal film by,for example, electroplating. Subsequently, unwanted barrier metal andinterconnection metal films outside the interconnection trench 113 areremoved by CMP to form an interconnection 109 (FIG. 1( h)). Thus, asemiconductor device having a desired pattern can be reliably provided.

A light source used in lithography of a chemically amplified resist 101may be selected from, for example, KrF excimer laser, ArF excimer laser,F₂ excimer laser, EUV and EB.

The third interlayer insulating film 103 may be, for example, an SiO₂,SiOC, SiC or SiCN film. The second interlayer insulating film 104 andthe first interlayer insulating film 106 may be a lowdielectric-constant film made of a material with a lower dielectricconstant such as SiO₂, HSQ, MSQ, MHSQ, ladder-type hydrogenatedsiloxane, SiLK®, SiOF, SiOC, SiON and BCB (benzocyclobutene) films. Whenthe first interlayer insulating film 106 is a low dielectric-constantfilm, the film has a lower density than an SiO₂ film and thus tends toocclude an organic base such as an amine, but allows the chemicallyamplified resist 101 to be much more effective, suitably ensuringsensitivity and resolution of the resist pattern.

A ladder-type hydrogenated siloxane is a polymer having a ladder-likemolecular structure, which preferably has a dielectric constant of 2.9or less in the light of preventing interconnection delay. For example,preferably, the density of a lower film is from 1.50 g/cm² to 1.58 g/cm²and its refractive index (at 633 nm) is from 1.38 to 1.40. A specificexample of such a film material is L-Ox™ which is called a ladder oxide(hereinafter, referred to as “L-Ox”). An insulating material prepared bymaking an L-Ox porous can be also used.

The second etching stopper film 105 and the first etching stopper film107 may be, for example, an SiC, SiN, SiON or SiCN film. When the secondetching stopper film 105 or the first etching stopper film 107 is anitrogen-containing film, a basic component such as an amine tends topermeate into the second interlayer insulating film 104 or the firstinterlayer insulating film 106. However, when using such a film, achemically amplified resist 101 can be employed to allow a salt in thechemically amplified resist 101 to be more effective. The chemicallyamplified resist 101 can be more suitably used in a process for forminga resist pattern on an insulating film comprising a concave to be aninterconnection trench or a via-hole.

As described above, according to this embodiment, a chemically amplifiedresist 101 can be used to prevent poisoning of a resist and to improvesensitivity in lithography.

Embodiment 2

The interconnection structure in FIG. 1( h) may be also manufactured bya so-called trench-first method among dual damascene processes. Therewill be described a copper interconnection structure manufactured by atrench-first method with reference to FIG. 2. In this embodiment,similar components to those in Embodiment 1 are identified with the samesymbols without any description as appropriate.

As described in Embodiment 1, on a lower interconnection layer 108 aresequentially deposited a first etching stopper film 107, a firstinterlayer insulating film 106, a second etching stopper film 105, asecond interlayer insulating film 104 and a third interlayer insulatingfilm 103. Then, using well-known lithography and etching technique, aninterconnection trench 113 is formed in the third interlayer insulatingfilm 103 and the second interlayer insulating film 104 (FIG. 2( a)).

Then, an anti-reflection film 102 is formed on the third interlayerinsulating film 103 and the second etching stopper film 105, duringwhich the interconnection trench 113 is partly or totally buried withthe anti-reflection film 102. This Figure shows that the interconnectiontrench 113 is partly buried with the anti-reflection film 102 (FIG. 2(b)).

Next, on the anti-reflection film 102 is applied a chemically amplifiedresist 101 (FIG. 2( c)). Herein, the resist composition described inEmbodiment 1 is used as the chemically amplified resist 101. Then, inthe chemically amplified resist 101 is formed an opening pattern 122 forforming a via-hole connected between the interconnection trench 113 anda lower interconnection layer 108 (FIG. 2( d)).

Subsequently, using the chemically amplified resist 101 as a mask, theanti-reflection film 102 on the second etching stopper film 105, andthen the second etching stopper film 105 and the first interlayerinsulating film 106 are etched off to form a via-hole 111 (FIGS. 2( e)and (f)).

Then, the chemically amplified resist 101 and the anti-reflection film102 are stripped off by O₂ plasma ashing and using an organic stripper.Next, the first etching stopper film 107 at the bottom of the via-hole111 is etched off to provide a structure where the via-hole 111 isconnected to the upper surface of the interconnection metal (not shown)in the lower interconnection layer 108 (FIG. 2( g)). FIG. 2( g) showsthe same structure as that in FIG. 1( g), so that an interconnection 109can be formed as described in Embodiment 1 in subsequent processes (FIG.2( h)).

As described above, in a trench-first process, a chemically amplifiedresist 101 can be also used to prevent poisoning of a resist and toimprove sensitivity in lithography.

Embodiment 3

The resist composition used in Embodiment 1 or 2 can be applied to avia-first dual damascene process using a three-layer resist method.There will be described this process with reference to FIG. 3.

First, on a lower interconnection layer 108 are sequentially deposited afirst etching stopper film 107 and an interlayer insulating film 115.Then, using well-known lithography and etching technique, a via-hole 111is formed in the interlayer insulating film 115 (FIG. 3( a)).

Then, an anti-reflection film (not shown) is formed on the interlayerinsulating film 115 and the first etching stopper film 107, during whichthe via-hole 111 is partly or totally buried with the anti-reflectionfilm. Then, on the anti-reflection film is applied a three-layer resistfilm consisting of a first resist film 116, a second resist film 117 anda third resist film 118, in which the first resist film 116 comprisesthe resist composition described above. Then, in the third resist film118 is formed an opening pattern 119 for forming an interconnectiontrench connected to the via-hole 111 (FIG. 3( b)).

Subsequently, using the third resist film 118 as a mask, the secondresist film 117 is etched off (FIG. 3( c)).

Then, the third resist film 118 is stripped off by O₂ plasma ashing andusing an organic stripper, during which the upper part of the firstresist film 116 is partly removed (FIG. 3( d)). Next, using the secondresist film 117 as a mask, the first resist film 116 on the interlayerinsulating film 115 and the interlayer insulating film 115 aresequentially etched off to form an opening pattern 119 (FIGS. 3( e) and(f)). Then, the first resist film 116 and the anti-reflection film (notshown) are stripped off by O₂ plasma ashing and using an organicstripper (FIG. 3( g)). Then, the first etching stopper film 107 at thebottom of the via-hole 111 is etched off to provide a structure wherethe via-hole 111 is connected to the upper surface of theinterconnection metal (not shown) in the lower interconnection layer 108(FIG. 3( h)).

Next, a metal film is formed such that it buries the opening pattern 119(that is, the interconnection trench 113) and the via-hole 111. Themetal film can be formed by first forming a barrier metal film 120within the interconnection trench 113 and the via-hole 111 by sputteringand then burying the interconnection trench 113 and the via-hole 111with an interconnection metal film 121 by, for example, electroplating(FIG. 3( i)). Subsequently, the unwanted barrier metal film 120 and theinterconnection metal film 121 outside the interconnection trench 113are removed by CMP to form an interconnection 109 (FIG. 3( j)).

In this embodiment, the first resist film 116 comprises a saltexhibiting buffer effect, so that a highly sensitive patterning can beachieved for the first resist film 116 even after patterning the secondresist film 117 and the third resist film 118.

This invention has been described with reference to some embodiments.The person skilled in the art will easily appreciate that theseembodiments are only illustrative and there may be a variety ofmodifications, all of which are encompassed by this invention.

Although a resist composition has been described in terms of a processused in a dual damascene process, it may be applied to anothersemiconductor process or other processes such as a manufacturing processfor a reticule. In such a case, on a chromium film may be, for example,patterned a chemically amplified resist, which may be used as a mask forforming an opening with a desired shape.

The resist composition in this embodiment can increase an exposuremargin without adding a quencher. It can be, therefore, applied to notonly lithography using a chemically amplified resist, but also anothertype of resist such as a resist for EB (electron beam) exposure. In thelatter resist, a pattern with improved sensitivity and resolution can bealso attained.

EXAMPLES Example 1

In this example, there was studied the action of a quencher in a resistcomposition. As a model for a resist composition, a solution of a givenamount of a quencher in a non-aqueous solvent was used and pH shift wasdetermined by titration when adding an acid generated from a photo-acidgenerator.

Specifically, acetonitrile and triethanolamine were used as anon-aqueous solvent and a quencher, respectively. To a given amount oftriethanolamine in acetonitrile solution (100 mL) was added dropwise0.1M p-toluenesulfonic acid solution in acetonitrile by 0.05 mL, usingan automatic titrator (Hiranuma Autotitrator COM-980Win; HIRANUMA SANGYOCo. Ltd.). Table 1 shows the compositions of the samples titrated. Inthis table, 1 mM monoethanolamine was added to Sample Nos. 2, 4, 6 and8, as a model for a system comprising a quencher in acetonitrile in aresist composition, into which an amine permeated.

Table 1 also shows a point of neutralization determined for each sample.Titration curves for the individual samples are shown in FIGS. 4 and 5.FIG. 5 is an enlarged view of a pH range of 8.5 to 10 in the titrationcurves for the samples.

TABLE 1 Quencher External amine Point of Sample Model Modelneutralization number compound mM compound mM mM 1 N(C₂H₄OH)₃ 0.0NH₂C₂H₄OH 0.0 0.0 2 N(C₂H₄OH)₃ 0.0 NH₂C₂H₄OH 1.0 1.0 3 N(C₂H₄OH)₃ 4.0NH₂C₂H₄OH 0.0 4.0 4 N(C₂H₄OH)₃ 4.0 NH₂C₂H₄OH 1.0 5.0 5 N(C₂H₄OH)₃ 8.0NH₂C₂H₄OH 0.0 8.0 6 N(C₂H₄OH)₃ 8.0 NH₂C₂H₄OH 1.0 9.1 7 N(C₂H₄OH)₃ 12.0NH₂C₂H₄OH 0.0 12.0 8 N(C₂H₄OH)₃ 12.0 NH₂C₂H₄OH 1.0 13.1

These results indicate the followings.

The quencher mechanism in the prior art has proposed that a quenchercauses deprotonation represented by formula (1), resulting in buffereffect.

—NH⇄—N+H  (1)

However, the equilibrium reaction in formula (1) does not easily movetoward the right side. The pKa of conjugated acid of amines is usuallymuch higher than the pKa of acids. For example, the pKa of conjugatedacid of triethanolamine is 15.9, while the pKa of p-toluenesulfonic acidis 8.7 in acetonitrile at 25° C. (Kimisuke Izutsu, “Hisuiyoueki noDenkikagaku (Electrochemistry in Nonaqueous solutions)”, edited byBaihukan, 1995, p. 48 and 53). Therefore, in formula (1) under acidicconditions where a photoacid generator exists, it can be assumed thatdissociation of a proton attached to an amine may be almost negligible.

Categorizing the results in Table 1 and FIG. 4 in accordance withrelationship between a quencher concentration in a sample (C_(b)) and aconcentration of an acid added into the sample (C_(a)), the following(i) to (iii) have been found.

(i) C_(b)>C_(a)

When a quencher concentration in a sample (C_(b)) is larger than an acidadded into the sample (C_(a)), i.e., in an initial range in thetitration curve, the quencher base is neutralized by the acid added asdemonstrated by equation (2):

R₃N+HA→R₃NHA  (2)

wherein R represents C₂H₄OH in triethanolamine; and A representsCH₃C₆H₄SO₃ ⁻ group in p-toluenesulfonic acid.

(ii) C_(b)=C_(a)

A neutralization point in each titration curve shown in FIG. 4corresponds to, as shown in Table 1, the total base concentration, i.e.,the sum of a quencher concentration and an external amine concentration.In samples 1, 3, 5 and 7 without an external amine, an acid at the sameconcentration as an initial concentration of the quencher C_(b) is usedfor neutralization.

In a practical resist composition, as a neutralization point is higher,a concentration of the acid used in the reaction of formula (2) isincreased, resulting in reduction of a concentration ratio of an acidgenerated from a photoacid generator which can act on a photosensitivepolymer. When this neutralization point is fluctuated due to thepresence of an external amine, a concentration of the acid which can acton a photosensitive polymer varies, so that a wide exposure margincannot be set, which is undesirable in the light of reliably conductinglithography.

(iii) C_(a)>C_(b)

FIG. 4 demonstrates that in a sample without an external amine, as aconcentration of an acid added (C_(a)) increases, a pH rapidly reducesand after a neutralization point, a proton concentration [H⁺]significantly increases. In this range, an equilibrium expressed byequation (3) is effective, where the acid is dissociated and then movedto a matrix M for protons. In this equation, the matrix M isacetonitrile.

HA+M→M→+A⁻  (3)

An equilibrium constant Kc in equation (3) can be expressed as equation(4) using an activity “a”, and under approximation that the “a” is equalto a molar concentration, the equation constant Kc can be expressed byequation (5):

$\begin{matrix}{{Kc} = \frac{{a\left( H^{+} \right)}{a\left( A^{-} \right)}}{{a({HA})}{a(M)}}} & (4) \\{{Kc} = \frac{\left\lbrack H^{+} \right\rbrack \left\lbrack A^{-} \right\rbrack}{\lbrack{HA}\rbrack \lbrack M\rbrack}} & (5)\end{matrix}$

Assuming that [MH⁺]<<[M] and [M] is a constant in equation (5), equation(6) can be derived, where an acid dissociation constant K_(a) is equalto a constant Kc[M].

$\begin{matrix}{{Ka} = {{{Kc}\lbrack M\rbrack} = \frac{\left\lbrack H^{+} \right\rbrack \left\lbrack A^{-} \right\rbrack}{\lbrack{HA}\rbrack}}} & (6)\end{matrix}$

When a dissociation equation of an acid is expressed by equation (7), anacid dissociation constant Ka can be expressed by equation (8). Asdescribed above, the pKa (=−log Ka) of p-toluenesulfonic acid inacetonitrile at 25° C. is 8.7 (Ka≈2.0×10⁻⁹), the equilibrium reaction inequation (3) is substantially shifted to the left.

HA⇄H⁺+A⁻  (7)

$\begin{matrix}{{Ka} = \frac{\left\lbrack H^{+} \right\rbrack \left\lbrack A^{-} \right\rbrack}{\lbrack{HA}\rbrack}} & (8)\end{matrix}$

Furthermore, a neutralization reaction of a quencher with an acid causesan equilibrium expressed by equation (9), resulting in increase of adissociated anion concentration [A⁻]. Thus, the acid dissociationequilibrium of equation (3) is further shifted to the left.

R₃NHA⇄(R₃NH⁺,A⁻)_(solv)⇄R₃NH⁺ _(solv)+A⁻ _(solv)  (9)

FIG. 4 demonstrates that the higher a concentration of the quencherinitially added, the more a salt is generated in the system. A higher pHin the range of C_(a)>C_(b), therefore, confirms the above description.

These (i) to (iii) suggest that a system comprising a quencher behavesas an equilibrium system in an aqueous solution. The range in (iii)corresponds to the fact that an acidic buffer solution contains a weakacid or conjugate base to a weak acid. Thus, there will be discussed amechanism for action of a quencher as a buffer when a sample iscontaminated with a basic component.

In this example, a basic component used was monoethanolamine. Samples 2,4, 6 and 8 comprise 1 mM monoethanolamine as an external amine and anequivalent concentration of a quencher, corresponding to samples 1, 3, 5and 7 without monoethanolamine, respectively. FIG. 5 is a partialenlarged view of FIG. 4 for more clearly demonstrating difference in anacidic range in a titration curve, depending on presence or absence ofan external amine.

When an external amine NRH₂ is added to a buffer system, a reactionexpressed by equation (10) is initiated. A large amount of theundissociated acid HA is present in the buffer system, which is bound tothe external amine to prevent pH shift.

RN₂H+HA→RN₃H+A⁻  (10)

It is assumed that in a sample comprising the external amine in FIG. 5,a neutralization point (C_(b)=C_(a)), i.e., a proton concentration [H⁺]required for an effective acid to be present in a photopolymer in apractical system, is a point of pH=9. It can be thus found that thehigher a quencher concentration is, the less a pH shift, ΔpH, in FIG. 5is. It is, therefore, confirmed that significant buffering action iseffective in the model of this invention comprising a quencher.

Next, effect in a system comprising a quencher will be simulated usingan equation for an acid dissociation constant. In the range ofC_(a)>C_(b) for acid dissociation equilibrium expressed by equation (7),there is a relationship expressed by equations (11) to (13), assumingthat a concentration of an ionized acid is x moles.

[HA]=C_(a)−C_(b) −x  (11)

[H⁺ ]=x  (12)

[A⁻]=C_(b) +x  (13)

From the above relationship, the salt formed by neutralization of thequencher with the acid, R₃NHA (equation (2)) can be assumed to becompletely dissociated in the system. Under this assumption, A⁻ derivedfrom the salt is equal to the quencher concentration C_(b) and the totalof A⁻ present in the system is the sum of C_(b) and x, wherein x is aconcentration of dissociated A⁻ in equation (7).

In this assumption, contribution of self-ionization of the matrix M or areaction of the matrix M with the anion A⁻ is probably negligible, sothat these factors are neglected. p-Toluenesulfonic acid ishomoconjugated to some extent in acetonitrile, but for simplifying themodel herein, a homoconjucation reaction between the anion A⁻ and HAexpressed by equation (14) is also neglected.

HA+A−⇄HA₂ ⁻  (14)

Assuming that x is so small to allow approximation ofC_(a)−C_(b)−x≈C_(a)−C_(b) and C_(b)−x≈C_(b), equation (8) for an aciddissociation constant can be expressed as equation (15). Therefore,under simplification that an activity of hydrogen ion is equal to itsmolar concentration, a pH is expressed by equation (16) from equation(15).

$\begin{matrix}{\left\lbrack H^{+} \right\rbrack = {{Ka}\; \frac{C_{a} - C_{b}}{C_{b}}}} & (15) \\{{pH} = {{- {\log \left\lbrack H^{+} \right\rbrack}}\mspace{31mu} = {{{{- \log}\; {Ka}} - {\log \; \frac{C_{a} - C_{b}}{C_{b}}}}\mspace{31mu} = {{pKa} - {\log \; \frac{C_{a} - C_{b}}{C_{b}}}}}}} & (16)\end{matrix}$

When a concentration of an external amine in the system is C_(e),fluctuation of a hydrogen-ion concentration and a pH′ are studied asdescribed above, obtaining equations (17) and (18).

$\begin{matrix}{\left\lbrack H^{+} \right\rbrack^{\prime} = {{Ka}\; \frac{C_{a} - C_{b} - C_{e}}{C_{b} + C_{e}}}} & (17) \\{{pH}^{\prime} = {{- {\log \left\lbrack H^{+} \right\rbrack}^{\prime}}\mspace{40mu} = {{pKa} - {\log \; \frac{C_{a} - C_{b} - C_{e}}{C_{b} + C_{e}}}}}} & (18)\end{matrix}$

Thus, subtracting equation (16) from equation (18), equation (19) for apH shift, ΔpH, due to incorporation of an external amine is obtained.

$\begin{matrix}{{\Delta \; {pH}} = {{{pH}^{\prime} - {pH}} = {\log \left( {1 + \frac{C_{a}C_{e}}{C_{b}\left( {C_{a} - C_{b} - C_{e}} \right)}} \right)}}} & (19)\end{matrix}$

As described above, equation (19) holds only when the total of the acidis smaller than the sum of the quencher and the external amine, i.e.,when C_(a)−C_(b)−C_(e)>0. Under these conditions, equation (19) clearlydemonstrates that as a quencher concentration increases, pH shift isreduced.

FIG. 6 shows a calculated ΔpH at pH=9 and ΔpH obtained from FIG. 5. Whendetermining a calculated value in FIG. 6, C_(a)=1.5×C_(b) because a pKaof p-toluenesulfonic acid is 8.7. FIG. 6 demonstrates that theexperimental values are in excellent agreement with the calculatedvalues. It may confirm that equation (19) is valid as an approximation.

From the above investigation, the followings have been found. Generally,in a resist composition, an acid derived from a photoacid generator usedis a substance corresponding to a strong acid in an aqueous solution. Ithas been, however, found that in acetonitrile, an organic solvent, suchan acid exhibits a smaller dissociation ratio and when adding a salthaving buffer effect to acetonitrile, equilibrium is established.Acetonitrile is an aprotic and non-aqueous solvent with a higherdielectric constant, so that it behaves as if such equilibrium isestablished in a practical resist composition.

Example 2

In this example, a solution of predetermined amounts of a quencher andof a salt in a non-aqueous solvent was used as a resist compositionmodel, and pH shift after adding an acid generated from a photoacidgenerator was determined by titration.

Specifically, to samples 3 and 4 in Table 1 in Example 1 containing aquencher at 4 mM was further added triethanolamine p-toluenesulfonate(formula (H)) to 12 mM, and the resulting samples were subjected to pHtitration as described in Example 1. The titration curves obtained werecompared with those for samples 3 and 4, respectively.

FIGS. 7 and 8 are titration curves for these samples. FIG. 8 is anenlarged view of the pH=8 to 12 region in the titration curves in FIG.7. FIG. 7 demonstrates that comparing presence of the salt for thesamples containing a quencher at 4 mM, addition of the salt reducesfluctuation before and after the neutralization point. It may be thusexpected that in a practical resist composition, fluctuation in a systempH can be also minimized by addition of a salt, resulting in reducedfluctuation of lithography sensitivity and reliable patterning.

Furthermore, FIG. 7 demonstrates that by adding a salt, a pH curvebecomes flat in the above regions (i) and (iii), i.e., the region wherea quencher (base) or acid is excessive. It indicates that pH shiftassociated with variation in the amount of the acid in the system isprevented. It may be, therefore, expected that in a practical resistcomposition, fluctuation in solubility of a base polymer associated withvariation in the generated acid is prevented. Thus, even when anexposure varies in patterning a resist, a pattern can be reliablyformed, that is, a wider exposure margin can be attained by adding asalt.

Furthermore, FIG. 8 demonstrates that contamination with an externalamine causes a relatively larger pH shift in a system without a salt,while a pH shift is reduced even when being contaminated with anexternal amine in a system comprising a salt. It suggests thatfluctuation of neutralization due to contamination of a system with anamine is prevented because a salt added significantly exhibits buffereffect. It may be, therefore, expected that in a practical resistcomposition, an acid generated from a photoacid generator by exposurecan minimize reduction in an amount of an effective acid due toconsumption of the acid in neutralization of the external amine,allowing patterning with higher sensitivity.

Example 3

In this example, an interconnection structure was manufactured on asilicon substrate, using a dual damascene process by a via-first methoddescribed with reference to FIG. 1. Herein, a lower interconnectionlayer 108 was an SiO₂ film with a thickness of 300 nm without aninterconnection structure. A first etching stopper film 107 was an SiCNfilm with a thickness of 70 nm; a first interlayer insulating film 106was an SiO₂ film with a thickness of 600 nm; a second etching stopperfilm 105 was an SiC film with a thickness of 50 nm; a second interlayerinsulating film 104 was an L-Ox film with a thickness of 300 nm; a thirdinterlayer insulating film 103 was an SiO₂ film with a thickness of 250nm; and an anti-reflection film 102 was an anti-reflection film(Clariant Japan, KK.) with a thickness of 60 nm. The chemicallyamplified resist 101 had a thickness of 600 nm. The via-hole 111(diameter ca 200 nm) was formed by the well-known lithography andetching technique and then the resist for via-hole forming was removedby O₂ plasma ashing and an amine stripper.

The chemically amplified resist 101 comprised a positive KrF resistmainly made of a polyhydroxystyrene resist protected with an acetalprotecting group and bis(p-toluenesulfonyl)diazomethane (by Midorikagakuco.) as a photoacid generator. Then, the following three differentcompositions were prepared as shown in Table 2. In sample (c), a saltwas the compound represented by formula (F):

(a) a composition prepared by adding a normal amount of quencher to acommercially available resist composition (quencher amount=1 in Table2);

(b) a composition prepared by adding an excessive amount of quencher toa commercially available resist composition (quencher amount=5 in Table2); and

(c) a composition prepared by adding, in addition to a quencher, a saltto an amount of 0.05 mole per 1 kg of a resist polymer to a commerciallyavailable resist composition (quencher amount=1, an amount of the saltadded=4 in Table 2).

Using each of samples from (a) to (c) as a chemically amplified resist101, KrF laser exposure was conducted to form an interconnection trenchpattern extending to one direction. The exposure conditions wereNA=0.75, σ=0.75 and in normal mode. Table 2 shows the patterningconditions and the results. An interconnection trench pattern formedusing a KrF resist was observed the resist pattern over a via byscanning electron microscopy (SEM). FIG. 9 shows the resulting SEMphotograph.

For an ArF-exposure and an EB-exposure resists, compositionscorresponding to (a) to (c) for each resist were also prepared andevaluated as well. Table 2 shows the patterning conditions and theresults.

The ArF-exposure resist was mainly made of an acrylate type ArF resistand a triphenylsulfonium p-toluenesulfonate as a photoacid generator. Insample (c), the compound represented by formula (G) was used as a salt.Exposure was conducted using a KrF laser at a wavelength of 193 nm underthe conditions of NA=0.72, σ=0.75 and in normal mode.

In terms of the EB-exposure resist, a negative resist was mainly made ofa polyhydroxystyrene resist whose OH groups were protected as alkylether and a photoacid generator comprisingbis(p-toluenesulfonyl)diazomethane and triphenylsulfoniump-toluenesulfonate. In sample (c), a salt was the compound representedby formula (H). Exposure was conducted by direct drawing with 100 KeVelectron beam.

A positive resist was mainly made of a cresol novolac resin, a melaminecrosslinking agent and a photoacid generator comprisingbis(p-toluenesulfonyl)diazomethane and triphenylsulfoniump-toluenesulfonate. In sample (c), a salt was the compound representedby formula (H). Exposure was conducted by straight-writing drawing with50 KeV electron beam.

TABLE 2 Pattern Amount size (nm) Exposure Light (Relative value) Line/margin source Type Quencher Salt Space (CD ± 10%) KrF Positive a 1 0140/140 11% excimer b 5 0 140/140 15% laser c 1 4 140/140 16% (248 nm)ArF Positive a 1 0 100/100 16% excimer b 5 0 100/100 21% laser c 1 4100/100 23% (193 nm) EB Negative a 1 0 100/100 8% (100 KeV) b 5 0100/100 13% c 1 4 100/100 15% EB Positive a 1 0 100/100 7% (50 KeV) b 50 100/100 14% c 1 4 100/100 24% Resist poisoning in a Light Sensitivity/via-first process source Type cm² (3-layer resist process) KrF Positivea 52 mJ Defective resolution excimer b 310 mJ No defects laser c 40 mJNo defects (248 nm) ArF Positive a 30 mJ Defective resolution excimer b160 mJ No defects laser c 28 mJ No defects (193 nm) EB Negative a 9 μCDefective resolution (100 KeV) b 45 μC No defects c 11 μC No defects EBPositive a 7 μC Defective resolution (50 KeV) b 36 μC No defects c 6 μCNo defects

Hole patterning was also evaluated as described for patterning of aninterconnection trench. Table 3 shows the patterning conditions and theresults.

TABLE 3 Additive Pattern Exposure Light (Relative value) size marginSensitivity/ source Type Quencher Salt (nm) (CD ± 10%) cm² KrF Positivea 1 0 140 10% 60 mJ excimer laser b 5 0 140 15% 320 mJ c 1 4 140 15% 56mJ (248 nm) ArF Positive a 1 0 120 17% 25 mJ excimer b 5 0 120 24% 130mJ laser c 1 4 120 25% 24 mJ (193 nm) EB Positive a 1 0 100 6% 9 μC (50KeV) b 5 0 100 11% 45 μC c 1 4 100 12% 8 μC

As seen from Tables 2 and 3, with a usual amount of a quencher,sensitivity was good, but an exposure margin was too small to attainadequate resolution. With an excessive amount of a quencher, an exposuremargin was increased while sensitivity was lowered. In a systemcomprising both a quencher and a salt, sensitivity and resolution weregood and an exposure margin was adequate.

FIG. 9( a) to (c) shows an SEM photograph after KrF excimer laserexposure using resist compositions (a) to (c), respectively. From FIG.9( a), it can be observed that defective resolution due to resistpoisoning occurred for a commercially available resist comprising anormal amount of a quencher. FIG. 9( b) indicates that when using aresist composition comprising an excess amount of a quencher, patterningwas satisfactorily but sensitivity is not adequate, and thus there isroom for improvement in the light of mass-productiveness. In contrast,FIG. 9( c) indicates that when adding, in addition to a quencher, a saltcomprising a conjugate base to an acid, patterning was satisfactory andsensitivity was not deteriorated.

These results confirm that a resist comprising a quencher and a saltcomprising a conjugate base to an acid can be used to prevent poisoningor sensitivity deterioration and to attain improved patterning.

As described above, according to this invention, a resist compositioncomprising a salt exhibiting buffer effect can be used to preventpoisoning in a chemically amplified resist.

1. A process for manufacturing a semiconductor device, comprising thesteps of; forming a film to be etched on a semiconductor substrate,applying a chemically amplified resist composition on the film to beetched to form a resist film, patterning the resist film and etching thefilm to be etched, using the patterned resist film as a mask: whereinthe chemically amplified resist composition comprises; a base resin, aphotoacid generator which generates an acid by exposure, and a saltexhibiting buffer effect in the base resin.
 2. A process formanufacturing a semiconductor device, comprising the steps of; forming afilm to be etched on a semiconductor substrate, on the film to beetched, forming a first resist film patterned in a predetermined shapeand using the first resist film as a mask, etching the film to be etchedto form a concave, removing the first resist film, on the film to beetched, applying a chemically amplified resist composition, which isthen dried to form a second resist film, patterning the second resistfilm to form an opening such that at least part of the region where theconcave has been formed is exposed, and etching the film to be etched,using the patterned second resist film as a mask: wherein the chemicallyamplified resist composition comprises; a base resin, a photoacidgenerator which generates an acid by exposure, and a salt exhibitingbuffer effect in the base resin.
 3. The process for manufacturing asemiconductor device as claimed in claim 2, wherein the step of removingthe first resist film comprises removing a part of the first resist filmwith an amine stripper.
 4. The process for manufacturing a semiconductordevice as claimed in claim 1, wherein the film to be etched containsnitrogen.
 5. The process for manufacturing a semiconductor device asclaimed in claim 2, wherein the film to be etched contains nitrogen. 6.The process for manufacturing a semiconductor device as claimed in claim1, wherein the film to be etched is a film having a porous structurewith a specific dielectric constant of 3 or less.
 7. The process formanufacturing a semiconductor device as claimed in claim 2, wherein thefilm to be etched is a film having a porous structure with a specificdielectric constant of 3 or less.
 8. The process for manufacturing asemiconductor device as claimed in claim 1, wherein the salt comprisesthe acid generated from the photoacid generator by exposure.
 9. Theprocess for manufacturing a semiconductor device as claimed in claim 2,wherein the salt comprises the acid generated from the photoacidgenerator by exposure.
 10. The process for manufacturing a semiconductordevice as claimed in claim 1, wherein the salt is a sulfonate.
 11. Theprocess for manufacturing a semiconductor device as claimed in claim 2,wherein the salt is a sulfonate.
 12. The process for manufacturing asemiconductor device as claimed in claim 1, wherein the salt is an aminesalt.
 13. The process for manufacturing a semiconductor device asclaimed in claim 2, wherein the salt is an amine salt.
 14. The processfor manufacturing a semiconductor device as claimed in claim 1, whereinthe salt is a salt of an alkanolamine or alkoxyalkylamine with asulfonic acid.
 15. The process for manufacturing a semiconductor deviceas claimed in claim 2, wherein the salt is a salt of an alkanolamine oralkoxyalkylamine with a sulfonic acid.
 16. The process for manufacturinga semiconductor device as claimed in claim 1, wherein the base resin isa resin whose alkali solubility is changed by the action of the acid.17. The process for manufacturing a semiconductor device as claimed inclaim 2, wherein the base resin is a resin whose alkali solubility ischanged by the action of the acid.
 18. A process for forming a pattern,comprising the steps of; applying a chemically amplified resistcomposition on a material to be etched to form a resist film, patterningthe resist film, and etching and patterning the material to be etched,using the patterned resist film as a mask: wherein the chemicallyamplified resist composition comprises; a base resin, a photoacidgenerator which generates an acid by exposure, and a salt exhibitingbuffer effect in the base resin.
 19. The process for patterning asclaimed in claim 18, wherein the material to be etched containsnitrogen.
 20. The process for patterning as claimed in claim 18, whereinthe film to be etched is a film having a porous structure with aspecific dielectric constant of 3 or less.
 21. The process forpatterning as claimed in claim 18, wherein the salt comprises the acidgenerated from the photoacid generator by exposure.
 22. The process forpatterning as claimed in claim 18, wherein the salt is a sulfonate. 23.The process for patterning as claimed in claim 18, wherein the salt isan amine salt.
 24. The process for patterning as claimed in claim 18,wherein the salt is a salt of an alkanolamine or alkoxyalkylamine with asulfonic acid.
 25. The process for patterning as claimed in claim 18,wherein the base resin is a resin whose alkali solubility is changed bythe action of the acid.